Polyolefin-substituted amines grafted with poly (aromatic-N-monomers) for oleaginous compositions

ABSTRACT

Novel polymers comprising polyolefin-substituted amines grafted with aromatic N-containing monomers such as aniline, have been found to provide oil soluble polymers having dispersant and antioxidant properties in oleaginous compositions, including fuel and lubricating oils. The polymers of this invention are further useful in electrical applications. These materials are formed by a process which comprises: (a) contacting an amine compound having at least two reactive nitrogen moieties with at least one long chain hydrocarbon-substituted reactant in an amount and under conditions sufficient to form a N-containing polymer adduct containing reactive amine groups, and (b) contacting the N-containing polymer adduct with at least one aromatic N-containing monomer under polymerization conditions to graft said N-containing polymer adduct with aromatic N-containing polymer segments. The long chain hydrocarbon-substituted reactant can comprise materials such as (i) long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups; (ii) halogenated long chain hydrocarbons; (iii) mixtures of formaldehyde and a long chain hydrocarbyl substituted phenol; and (iv) mixtures of formaldehyde and a reaction product formed by reaction of long chain hydrocarbons substituted with mono- or dicarboxylic acid, anhydride or ester groups and an amino-substituted, optionally hydrocarbyl-substituted phenol.

This is a division of application Ser. No. 08,668,313, filed on Jun. 26,1990, now U.S. Pat. No. 5,633,326, which is a continuation of Ser. No.07/997,631, filed on Dec. 28, 1992, now abandoned, which is acontinuation of Ser. No. 07/450,036, filed on Dec. 12, 1989, nowabandoned.

FIELD OF THE INVENTION

The present invention relates to a process for forming an oil-solublepolyaniline-grafted polyolefin polymers useful as dispersant andantioxidant additives for oleaginous compositions and also useful aselectrically conducting polymers in electrical applications.

BACKGROUND OF THE INVENTION

Polyaniline is one of the oldest polymers known, and has been preparedin the form of emeraldine hydrochloride by oxidizing an aqueoushydrochloric acid solution of aniline with ammonium peroxy disulfate atambient temperature. Polyaniline is a cheap, highly electricallyconducted polymer, but is processable with difficulty in its powderform. Conventionally, making such conjugated conducting polymersoil-soluble and processible has been a very difficult problem.

S. Li et al., Synth. Met. 20(2), 141-9 (1987) discloses the graftpolymerization of polyaniline with polyaminostyrene to form polyanilinesoluble in common organic solvents (DMF and DMSO, and slightly solublein methanol and trichloromethane). This procedure involved the nitrationof polystyrene (of 120,000 molecular weight) with either fuming nitricacid or a chloroform solution of 100% nitric acid and acetic anhydride.The resulting polynitrostyrene was hydrogenated with phenylhydrazineunder nitrogen to form the polyaminostyrene.

S. Li, "Synthesis and Characterization of Soluble Polyaniline," Syn.Met. 29 (E329-E336) (1989) reports three general synthetic routes forthe solubilization of polyaniline in DMF and DMSO. The experimentalsynthesis employed either formation of block polyaniline (employingeither para-aminobenzenesulfonylchloride/poly(ethylene glycol) reactionproducts or para-aminobenzoyl chloride/poly(ethylene glycol) reactionproducts, and the preparation of graft polyanilines by polymerization ofaniline on polyaminostyrene, polyacrylamides or polyepichlorohydrin.

S. P. Armes et al., "The Synthesis of Polymeric Surfactants for thePreparation of Sterically-Stabilized Polyaniline Colloids," Polym.Mater. Sci. Eng., 60, 751-753 (1989) discloses copolymerization of 2- or4-vinyl pyridine with para-aminostyrene.

T. Kobayashi et al., "Polyaniline Film-Coated Electrodes asElectrochromic Display Devices," J. Electroanal. Chem. 161, 419-423(1984) discloses evaluations of the electrochromic properties ofpolyaniline films.

A. G. MacDiarmid et al., "`Polyaniline`: Interconversion of Metallic andInsulating Forms," Mol. Cryst. Liq. Cryst., 121, 173-180 (1985)describes the synthesis of polyaniline powder and the conversion of thismaterial to various insulating and metallic forms by acid/base andoxidation/reduction mechanisms.

Y. Cao et al., "Spectroscopic and Electrical Characterization of SomeAniline Oligomers and Polyaniline," Syn. Met. 16, 305-315 (1986)describes the preparation of aniline oligomers and polyaniline, andproton-doped derivatives.

W. Huang et al., "Polyaniline, a Novel Conducting Polymer," J. Chem.Soc., Faraday Trans. 1, 82, 2385-2400 (1986) discloses the chemicalsynthesis of polyaniline and electrochemical synthesis of polyanilinefrom aniline.

F. L. Lu et al., "Phenyl-Capped Octaaniline (COA): An Excellent Modelfor Polyaniline," JACS 108, 8311-8313 (1986) discloses the preparationof a mono-dispersed polyaniline of molecular weight of 806 and itsconversion to a partially oxidized form.

F. Wudl et al., "Poly (p-phenyleneamine) Synthesis and Comparison toPolyaniline," JACS 109, 3677-3684 (1987) discloses the preparation ofsmall polyaniline oligomers by a double condensation of para-phenylamino-substituted anilines with diethyl succinoyl succinate and thepreparation of poly(p-phenaline amine) by the reaction of succinosuccinic acid (2,5-dioxo-1,4-cyclohexane dicarboxylic acid) andp-phenyline diamine.

A. G. MacDiarmid et al., "The Polyanilines: Processing, MolecularWeight, Oxidation State and Derivatives," Polymer Pre-prints 30, 147-48(1989); M. Angelopoulos et al. "Polyaniline: Solutions, Films andOxidation State," Mol. Cryst. Liq. Cryst. 160, 151-163 (1988); A.Andreatta et al., "Electrically-Conducted Fibers of Polyaniline SpunFrom Solutions in Concentrated Sulfuric Acid," Syn. Met. 26, 383-389(1988); A. Ray et al., "Polyaniline: Doping, Structure and Derivatives,"Synth. Met. 29, 141-150 (1989); S. P. Armes et al., "Novel ColloidalDispersions of Polyaniline," J. Chem. Soc., Chem. Commun. 88-89 (1989)also relate to preparation of polyaniline.

Y. Wei et al., "Synthesis and Electrochemistry of Alkyl Ring-SubstitutedPolyanilines," J. Phys. Chem. 93, 495-499 (1989) discloses the synthesisof poly(o-toluidine), poly(m-toluidine) and poly(o-ethylaniline), bychemical and electrochemical syntheses.

S. K. Manohar et al., "N-Substituted Derivatives of Polyaniline," Syn.Met. 29, 349-56 (1989) discloses the preparation of N-methylatedpolyaniline.

U.S. Pat. No. 4,604,427 relates to forming electrically conductingpolymer blends by impregnating a pre-formed host polymer with a cyclicmonomer such as aniline and then exposing the mixture with a chemicaloxidant to form the conductive polymer reaction product within thesurface layer of the host polymer.

Canadian Patent 806,736 relates to an antioxidant for hydrocarbon-typerubber which is in the form of an aromatic polymer having repeatingunits which consist of an NH-group attached to a difunctional aromaticgroup prepared by reacting either hydroquinone or para-benzoquinone withvarious aromatic diamines, such as para-phenylene diamine and2,7-diamino naphthylene (page 4). The antioxidant activity of exemplarypolymers were demonstrated in ethylene-propylene copolymer rubbervulcanisate (pages 7-8).

European Patent Publication 314,311 relates to the preparation ofconducting articles by (a) forming a gel of a carrier polymer in acompatible solvent, (b) polymerizing, within the gel, a selectedmonomer, and (c) doping the article so provided. Disclosed carrierpolymers include high molecular weight (M.W.>100,000) flexible chainpolymers, such as polyethylene, isostatic polypropylene, poly(ethyleneoxide) and polystyrene, and lower molecular weight polymers(10,000-100,000) having "rigid-rod" molecules, such as aramid polymers,aromatic polyesters, PBT and PBI. The polymerization step (b) caninclude oxidative-coupling polymerization employing aniline. Thepolymerization step results in the formation, within the carrierpolymer, of a normally intractable polymeric material derived from theselected monomer.

European Patent Publication 314,845 discloses graft copolymerscharacterized by oil-soluble substantially linear, carbon-carbonbackbone polymer having graft polymerized thereon units derived fromRNH₂ monomer, wherein R is a hydrocarbon containing a polymerizableethylenically unsaturated double bond. Illustrated amine monomersinclude p-aminostyrene and p-(aminomethyl) styrene.

U.S. Pat. No. 3,219,666 discloses lubricating oil dispersants comprisingoil-soluble, acylated nitrogen compositions, having within its structure(A) a substantially hydrocarbon-substituted polar group wherein thesubstantially hydrocarbon substituent contains at least about 50 carbonatoms, and (B) a nitrogen-containing group characterized by a nitrogenatom attached directly to the polar group and which are prepared, e.g.,by reacting a polyalkenyl-substituted succinic anhydride with an amine.Aniline and N-cyclohexyl-aniline are disclosed as amine reactants.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graphical plot of the solution electronic absorption spectraobtained using ultraviolet-visible spectroscopy as described in Example3.

SUMMARY OF THE INVENTION

The novel polymers of the present invention comprise nitrogen-containingpolymers, such as ashless nitrogen-containing dispersant (e.g.,polyisobutylene succinimides) and polyolefin-substituted amines, graftedwith aromatic N-containing monomers, such as aniline, to provide oilsoluble polymers having dispersant and antioxidant properties inoleaginous compositions, including fuel and lubricating oils. In fuels,the additives serve to minimize the degree of carburetor and fuelinjector fouling from deposits. The novel polymers are also useful inelectrically conductive devices.

In one embodiment of the invention, novel polymers are formed by (a)providing a N-containing polymer adduct containing reactive amino groupsformed by contacting an amine compound having at least two reactivenitrogen moieties with at least one long chain hydrocarbon-substitutedreactant in an amount and under conditions sufficient to form anitrogen-containing polymer adduct, said long chainhydrocarbon-substituted reactant comprising at least one member selectedfrom the group consisting of: (i) long chain hydrocarbons substitutedwith mono- or dicarboxylic acid, anhydride or ester groups; (ii)halogenated long chain hydrocarbons; (iii) mixtures of formaldehyde anda long chain hydrocarbyl substituted phenol; and (iv) mixtures offormaldehyde and a reaction product formed by reaction of long chainhydrocarbons substituted with mono- or dicarboxylic acid, anhydride orester groups and an amino-substituted, optionallyhydrocarbyl-substituted phenol, and (b) contacting said N-containingpolymer adduct with at least one aromatic N-containing monomer underpolymerization conditions to graft said N-containing polymer adduct witharomatic N-containing polymer segments.

In one preferred embodiment, the present invention is directed to apolyolefin-substituted dispersant and antioxidant additive useful inoleaginous compositions formed by (a) reacting in a liquid reactionmixture an amine compound having at least two reactive nitrogen moieties(e.g., ammonia or a polyamine such as a polyalkylene polyamine) with along chain hydrocarbyl substituted mono- or dicarboxylic acid materialcomprising a polyolefin, derived from a C₂ to C₁₀ monoolefin and havinga 300 to 10,000 number average molecular weight, substituted with atleast 0.5 (e.g., from about 1 to 4) mono- or dicarboxylic acid producingmoieties (preferably acid or anhydride moieties) per polyolefin moleculeto form an N-acylated polymer substituted adduct having reactive aminegroups, and (b) contacting said N-acylated polymer adduct with at leastone aromatic N-containing monomer under polymerization conditions tograft said N-acylated polymer adduct with an aromatic N-containingpolymer segments.

DETAILED DESCRIPTION OF THE INVENTION

AMINE COMPOUND

As described below, the N-containing polymer adduct employed in thepresent invention is prepared by contacting a long chain hydrocarbonsubstituted reactant with an amine compound containing at least two(e.g., from 2 to 20), preferably at least 3 (e.g., from 3 to 15), andmost preferably from 3 to 8, reactive nitrogen moieties (that is, thetotal of the nitrogen-bonded H atoms) per molecule of the aminecompound. The amine compound will generally comprise at least one memberselected from the group consisting of ammonia, organic primarymonoamines and organic polyamines containing at least one primary aminegroup or at least two secondary amine groups per molecule. Generally,the organic amines will contain from about 2 to 60, preferably 2 to 40(e.g. 3 to 20), total carbon atoms and about 2 to 12, preferably 3 to12, and most preferably from 3 to 8 (e.g., 5 to 9) total nitrogen atomsin the molecule. These amines may be hydrocarbyl amines or may behydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxygroups, amide groups, nitriles, imidazoline groups, and the like.Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxygroups are particularly useful. Preferred amines are aliphatic saturatedamines, including those of the general formulas: ##STR1## wherein R, R',R" and R'" are independently selected from the group consisting ofhydrogen; C₁ to C₂₅ straight or branched chain alkyl radicals; C₁ to C₁₂alkoxy C₂ to C₆ alkylene radicals; C₂ to C₁₂ hydroxy amino alkyleneradicals; and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals; andwherein R'" can additionally comprise a moiety of the formula: ##STR2##wherein R' is as defined above, and wherein s and s' can be the same ora different number of from 2 to 6, preferably 2 to 4; and t and t' canbe the same or different and are numbers of from 0 to 10, preferably 2to 7, and most preferably about 3 to 7, with the proviso that the sum oft and t' is not greater than 15. To assure a facile reaction, it ispreferred that R, R', R", R'", s, s', t and t' be selected in a mannersufficient to provide the compounds of Formulas I and II with typicallyat least one primary or secondary amine group, preferably at least twoprimary or secondary amine groups. This can be achieved by selecting atleast one of said R, R', R" or R'" groups to be hydrogen or by letting tin Formula II be at least one when R'" is H or when the III moietypossesses a secondary amino group.

Non-limiting examples of suitable organic amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetra; tetraethylene pentamine; polypropylene amines such as1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene)triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl)ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine;3-dodecyloxypropylamine; N-dodecyl-1,3-propane diamine; trishydroxymethylaminomethane (THAM); diisopropanol amine; diethanol amine;triethanol amine; mono-, di-, and tri-tallow amines; amino morpholinessuch as N-(3-aminopropyl)morpholine; and mixtures thereof.

Other useful amine compounds include: alicyclic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula (IV): ##STR3## wherein p₁ and P₂ are the same or different andare each integers of from 1 to 4, and n₁, n₂ and n₃ are the same ordifferent and are each integers of from 1 to 3. Non-limiting examples ofsuch amines include 2-pentadecyl imidazoline: N-(2-aminoethyl)piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. Forexample, one process for preparing alkylene amines involves the reactionof an involves the reaction of an alkylene dihalide (such as ethylenedichloride or propylene dichloride) with ammonia, which results in acomplex mixture of alkylene amines wherein pairs of nitrogens are joinedby alkylene groups, forming such compounds as diethylene triamine,triethylenetetra, tetraethylene pentamine and isomeric piperazines. Lowcost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogenatoms per molecule are available commercially under trade names such as"Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formulae:

    NH.sub.2 --alkylene--(--O--alkylene).sub.m --NH.sub.2      (V)

where m has a value of about 3 to 70 and preferably 10 to 35; and

    R.sup.4 -- --alkylene--(--O--alkylene)n.sub.4 --NH.sub.2 !.sub.p(VI)

where "n₄ " has a value of about 1 to 40 with the provision that the sumof all the n₄ 's is from about 3 to about 70 and preferably from about 6to about 35, and R⁴ is a polyvalent saturated hydrocarbon radical of upto ten carbon atoms wherein the number of substituents on the R⁴ groupis represented by the value of "p", which is a number of from 3 to 6.The alkylene groups in either formula (V) or (VI) may be straight orbranched chains containing about 2 to 7, and preferably about 2 to 4carbon atoms.

The polyoxyalkylene polyamines of formulas (V) or (VI) above, preferablypolyoxyalkylene diamines and polyoxyalkylene triamines, may have averagemolecular weights ranging from about 200 to about 4000 and preferablyfrom about 400 to about 2000. The preferred polyoxyalkylenepolyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.

Additional amines useful in the present invention are described in U.S.Pat. No. 3,445,441, the disclosure of which is hereby incorporated byreference in its entirety.

The amine compound can comprise an amido-amine formed by reacting apolyamine with an alpha, beta-ethylenically unsaturated compound (e.g.,of formula XXII), e.g. by reacting polyethylene amines (e.g.,tetraethylene pentaamine, pentaethylene hexamine, and the like),polyoxyethylene and polyoxypropylene amines, e.g., polyoxypropylenediamine, trismethylolaminomethane and pentaerythritol, and combinationsthereof, with with an acrylate-type compound, and most preferably withan acrylate-type reactant selected from the group consisting of loweralkyl alky-acrylates (e.g., methyl, ethyl, iso-propyl, propyl,iso-butyl, n-butyl, tert-butyl, etc., esters of methacrylic acid,acrylic acid, and the like).

Exemplary of such amido-amines are compounds of the formula:

    NH.sub.2  (CH.sub.2).sub.v NH!.sub.u C(O)C.sub.2 H.sub.4  NH(CH.sub.2).sub.v !.sub.u NH.sub.2

wherein u is an integer of from 1 to 10, and v is an integer of from 2to 6.

Most preferred as the amine compound are members selected from the groupconsisting of ammonia and organic diprimary amines having from 2 to 12carbon atoms and from 2 to 8 nitrogen atoms per molecule. Examples ofsuch preferred organic diprimary amines are ethylene diamine, propylenediamine, diethylene triamine, dipropylene triamine, triethylenetetraamine, tripropylene tetraamine, tetraethylene pentaamine,tetrapropylene pentaamine, polyhexamethylene diamine, phenyl diamine.

PREPARATION OF LONG CHAIN HYDROCARBYL SUBSTITUTED REACTANT

(A) The long chain hydrocarbyl polymer-substituted mono- or dicarboxylicacid material, i.e., acid, anhydride or acid ester used in thisinvention, includes the reaction product of a long chain hydrocarbonpolymer, generally a polyolefin, with a monounsaturated carboxylicreactant comprising at least one member selected from the groupconsisting of (i) monounsaturated C₄ to C₁₀ dicarboxylic acid(preferably wherein (a) the carboxyl groups are vicinyl, (i.e. locatedon adjacent carbon atoms) and (b) at least one, preferably both, of saidadjacent carbon atoms are part of said mono unsaturation); (ii)derivatives of (i) such as anhydrides or C₁ to C₅ alcohol derived mono-or di-esters of (i); (iii) monounsaturated C₃ to C₁ o monocarboxylicacid wherein the carbon-carbon double bond is conjugated to the carboxygroup, i.e, of the structure ##STR4## and (iv) derivatives of (iii) suchas C₁ to C₅ alcohol derived monoesters of (iii). Upon reaction with thepolymer, the monounsaturation of the monounsaturated carboxylic reactantbecomes saturated. Thus, for example, maleic anhydride becomes a polymersubstituted succinic anhydride, and acrylic acid becomes a polymersubstituted propionic acid.

Typically, from about 0.7 to about 4.0 (e.g., 0.8 to 2.6), preferablyfrom about 1.0 to about 2.0, and most preferably from about 1.1 to about1.7 moles of said monounsaturated carboxylic reactant are charged to thereactor per mole of polymer charged.

Normally, not all of the polymer reacts with the monounsaturatedcarboxylic reactant and the reaction mixture will contain non-acidsubstituted polymer. The polymer-substituted mono- or dicarboxylic acidmaterial (also referred to herein as "functionalized" polymer orpolyolefin), non-acid substituted polyolefin, and any other polymericby-products, e.g. chlorinated polyolefin, (also referred to herein as"unfunctionalized" polymer) are collectively referred to herein as"product residue" or "product mixture". The non-acid substituted polymeris typically not removed from the reaction mixture (because such removalis difficult and would be commercially infeasible) and the productmixture, stripped of any monounsaturated carboxylic reactant is employedfor further reaction with the amine or alcohol as described hereinafterto make the dispersant.

Characterization of the average number of moles of monounsaturatedcarboxylic reactant which have reacted per mole of polymer charged tothe reaction (whether it has undergone reaction or not) is definedherein as functionality. Said functionality is based upon (i)determination of the saponification number of the resulting productmixture using potassium hydroxide; and (ii) the number average molecularweight of the polymer charged, using techniques well known in the art.Functionality is defined solely with reference to the resulting productmixture. Although the amount of said reacted polymer contained in theresulting product mixture can be subsequently modified, i.e. increasedor decreased by techniques known in the art, such modifications do notalter functionality as defined above. The terms "polymer substitutedmonocarboxylic acid material" and "polymer substituted dicarboxylic acidmaterial" as used herein are intended to refer to the product mixturewhether it has undergone such modification or not.

Accordingly, the functionality of the polymer substituted mono- anddicarboxylic acid material will be typically at least about 0.5,preferably at least about 0.8, and most preferably at least about 0.9and will vary typically from about 0.5 to about 2.8 (e.g., 0.6 to 2),preferably from about 0.8 to about 1.4, and most preferably from about0.9 to about 1.3.

Exemplary of such monounsaturated carboxylic reactants are fumaric acid,itaconic acid, maleic acid, maleic anhydride, chloromaleic acid,chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid,cinnamic acid, and lower alkyl (e.g., C₁ to C₄ alkyl) acid esters of theforegoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, etc.

Preferred olefin polymers for reaction with the monounsaturatedcarboxylic reactants to form reactant A are polymers comprising a majormolar amount of C₂ to C₁₀, e.g., C₂ to C₅ monoolefin. Such olefinsinclude ethylene, propylene, butylene, isobutylene, pentene, octene-1,styrene, etc. The polymers can be homopolymers such as polyisobutylene,as well as copolymers of two or more of such olefins such as copolymersof: ethylene and propylene; butylene and isobutylene; propylene andisobutylene; etc. Mixtures of polymers prepared by polymerization ofmixtures of isobutylene, butene-1 and butene-2, e.g., polyisobutylenewherein up to about 40% of the monomer units are derived from butene-1and butene-2, is an exemplary, and preferred, olefin polymer. Othercopolymers include those in which a minor molar amount of the copolymermonomers, e.g., 1 to 10 mole %, is a C₄ to C₁₈ non-conjugated diolefin,e.g., a copolymer of isobutylene and butadiene; or a copolymer ofethylene, propylene and 1,4-hexadiene; etc.

In some cases, the olefin polymer may be completely saturated, forexample an ethylene-propylene copolymer made by a Ziegler-Nattasynthesis using hydrogen as a moderator to control molecular weight.

The olefin polymers used in the formation of reactant A will have numberaverage molecular weights within the range of about 300 to 10,000,generally from about 700 and about 5,000, preferably from about 1000 to4,000, more preferably between about 1300 and about 3,000. Particularlyuseful olefin polymers have number average molecular weights within therange of about 1500 and about 3000 with approximately one terminaldouble bond per polymer chain. An especially useful starting materialfor highly potent dispersant additives useful in accordance with thisinvention is polyisobutylene, wherein up to about 40% of the monomerunits are derived from butene-1 and/or butene-2. The number averagemolecular weight for such polymers can be determined by several knowntechniques. A convenient method for such determination is by gelpermeation chromatography (GPC) which additionally provides molecularweight distribution information, see W. W. Yau, J. J. Kirkland and D. D.Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons,New York, 1979.

The olefin polymers will generally have a molecular weight distribution(the ratio of the weight average molecular weight to number averagemolecular weight, i.e. M_(w) /M_(n)) of from about 1.0 to 4.5, and moretypically from about 1.5 to 3.0.

The polymer can be reacted with the monounsaturated carboxylic reactantby a variety of methods. For example, the polymer can be firsthalogenated, chlorinated or brominated to about 1 to 8 wt. %, preferably3 to 7 wt. % chlorine, or bromine, based on the weight of polymer, bypassing the chlorine or bromine through the polymer at a temperature of60° to 250° C., preferably 110° to 160° C., e.g. 120° to 140° C., forabout 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer maythen be reacted with sufficient monounsaturated carboxylic reactant at100° to 250° C., usually about 180° to 235° C., for about 0.5 to 10,e.g. 3 to 8 hours, so the product obtained will contain the desirednumber of moles of the monounsaturated carboxylic reactant per mole ofthe halogenated polymer. Processes of this general type are taught inU.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.Alternatively, the polymer and the monounsaturated carboxylic reactantare mixed and heated while adding chlorine to the hot material.Processes of this type are disclosed in U.S. Pat. Nos. 3,215,707;3,231,587; 3,912,764; 4,110,349; 4,234,435; and in U.K. 1,440,219.

Alternately, the polymer and the monounsaturated carboxylic reactant canbe contacted at elevated temperature to cause a thermal "ene" reactionto take place. Thermal "ene" reactions have been heretofore described inU.S. Pat. Nos. 3,361,673 and 3,401,118, the disclosures of which arehereby incorporated by reference in their entirety.

Preferably, the polymers used in this invention contain less than 5 wt%, more preferably less than 2 wt %, and most preferably less than 1 wt% of a polymer fraction comprising polymer molecules having a molecularweight of less than about 300, as determined by high temperature gelpremeation chromatography employing the corresponding polymercalibration curve. Such preferred polymers have been found to permit thepreparation of reaction products, particularly when employing maleicanhydride as the unsaturated acid reactant, with decreased sediment. Inthe event the polymer produced as described above contains greater thanabout 5 wt % of such a low molecular weight polymer fraction, thepolymer can be first treated by conventional means to remove the lowmolecular weight fraction to the desired level prior to initiating theene reaction, and preferably prior to contacing the polymer with theselected unsaturated carboxylic reactant(s). For example, the polymercan be heated, preferably with inert gas (e.g., nitrogen) stripping, atelevated temperature under a reduced pressure to volatilize the lowmolecular weight polymer components which can then be removed from theheat treatment vessel. The precise temperature, pressure and time forsuch heat treatment can vary widely depending on such factors as as thepolymer number average molecular weight, the amount of the low molecularweight fraction to be removed, the particular monomers employed andother factors. Generally, a temperature of from about 60° to 100° C. anda pressure of from about 0.1 to 0.9 atmospheres and a time of from about0.5 to 20 hours (e.g., 2 to 8 hours) will be sufficient.

In this process, the selected polymer and monounsaturated carboxylicreactant and halogen (e.g., chlorine gas), where employed, are contactedfor a time and under conditions effective to form the desired polymersubstituted mono- or dicarboxylic acid material. Generally, the polymerand monounsaturated carboxylic reactant will be contacted in aunsaturated carboxylic reactant to polymer mole ratio usually from about0.7:1 to 4:1, and preferably from about 1:1 to 2:1, at an elevatedtemperature, generally from about 120° to 260° C., preferably from about160° to 240° C. The mole ratio of halogen to monounsaturated carboxylicreactant charged will also vary and will generally range from about0.5:1 to 4:1, and more typically from about 0.7:1 to 2:1 (e.g., fromabout 0.9 to 1.4:1). The reaction will be generally carried out, withstirring for a time of from about 1 to 20 hours, preferably from about 2to 6 hours.

By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g.polyisobutylene will normally react with the monounsaturated carboxylicacid reactant. Upon carrying out a thermal reaction without the use ofhalogen or a catalyst, then usually only about 50 to 75 wt. % of thepolyisobutylene will react. Chlorination helps increase the reactivity.For convenience, the aforesaid functionality ratios of mono- ordicarboxylic acid producing units to polyolefin, e.g., 1.1 to 1.8, etc.are based upon the total amount of polyolefin, that is, the total ofboth the reacted and unreacted polyolefin, used to make the product.

The reaction is preferably conducted in the substantial absence of O₂and water (to avoid competing side reactions), and to this end can beconducted in an atmosphere of dry N₂ gas or other gas inert under thereaction conditions. The reactants can be charged separately or togetheras a mixture to the reaction zone, and the reaction can be carried outcontinuously, semi-continuously or batchwise. Although not generallynecessary, the reaction can be carried out in the presence of a liquiddiluent or solvent, e.g., a hydrocarbon diluent such as minerallubricating oil, toluene, xylene, dichlorobenzene and the like. Thepolymer substituted mono- or dicarboxylic acid material thus formed canbe recovered from the liquid reaction mixture, e.g., after stripping thereaction mixture, if desired, with an inert gas such as N₂ to removeunreacted unsaturated carboxylic reactant.

If desired, a catalyst or promoter for reaction of the olefin polymerand monounsaturated carboxylic reactant (whether the olefin polymer andmonounsaturated carboxylic reactant are contacted in the presence orabsence of halogen (e.g., chlorine)) can be employed in the reactionzone. Such catalyst of promoters include alkoxides of Ti, Zr, V and Al,and nickel salts (e.g., Ni acetoacetonate and Ni iodide) which catalystsor promoters will be generally employed in an amount of from about 1 to5,000 ppm by weight, based on the mass of the reaction medium.

The selected amine compound(s) are readily reacted with the selectedpolymer substituted mono- or dicarboxylic acid material, e.g. alkenylsuccinic anhydride, by heating an oil solution containing 5 to 95 wt. %of the polymer substituted dicarboxylic acid material to about 100° to250° C., preferably 125° to 175° C., generally for 1 to 10, e.g. 2 to 6hours until the desired amount of water is removed. The heating ispreferably carried out to favor formation of imides and/or amides,rather than salts. Generally from 1 to 5, preferably from about 1.5 to 3moles of mono- or dicarboxylic acid moiety content (e.g., grafted maleicanhydride or grafted acrylic acid content) is used per reactive nitrogenequivalent (preferably per equivalent of primary nitrogen) of the aminecompound.

Preferably, the polymer substituted mono- or dicarboxylic acid producingmaterial and amine compound will be contacted for a time and underconditions sufficient to form an adduct having within its structure, onaverage, at least 0.5 (e.g., from 0.5 to 20), and preferably at least 1(e.g., from 1 to 15) reactive amine groups (i.e., primary and/orsecondary amino groups) per molecule. The progress of this reaction canbe followed by infra-red analysis.

The dispersant-forming reaction can be conducted in a polar or non-polarsolvent (e.g., xylene, toluene, benzene and the like), and is preferablyconducted in the presence of a mineral or synthetic lubricating oil. (B)Also useful as long chain hydrocarbyl reactants to form the improveddispersants of this invention are halogenated long chain aliphatichydrocarbons (as shown in U.S. Pat. Nos. 3,275,554, 3,438,757,3,565,804, and 4,000,353, the disclosures of which are herebyincorporated by reference in their entirety) where the halogen group onthe halogenated hydrocarbon is displaced with the nitrogen-containingcompound in the subsequent reaction therewith.

For example, a polymer of a C₂ to C₅ monoolefin, e.g., polyethylene,polypropylene or polyisobutylene, wherein the polymer has an averagemolecular weight within the range of from 600 to about 3,000, preferablyfrom about 800 to about 2,500, is halogenated with either bromine orchlorine; preferably the latter. The halogen may be conveniently addedas gaseous chloride, liquid bromine, or a hydrohalogen, e.g., HCl or HBrgas.

The amount of halogen introduced will depend on the particularhydrocarbon used, the desired amount of amine to be introduced into themolecule, the particular alkylene amine used, and the halogen used. Theamount of halogen introduced will generally be in the range from about 1to 5 halogen atoms per molecule, depending on the reactivity of theresulting halide. On a weight percent basis, the amount of halide willgenerally range from about 1 to 25, more usually from about 1 to 10.

The halogenation step may be conducted in the temperature range of fromabout ordinary ambient temperatures to about 120° C. To aid in thehalogenation step, the polymer may be dissolved in a suitable solvent,such as carbon tetrachloride, in order to lower the viscosity of thepolymer, although the use of such a solvent is not necessary.

The time required for halogenation may be varied to some extent by therate at which the halogen is introduced. Ordinarily from about 2 toabout 5 hours is a satisfactory halogenation period. In a representativeplant scale operation involving the chlorination of polyisobutylene of830 molecular weight, a 100-pound batch will be chlorinated with 10pounds of chlorine introduced into the reactor over a period of 31/2hours with a chlorination temperature of about 120° C.

The halohydrocarbon and amine compound (e.g., alkylene polyamine orpolyalkylene polyamine) may be brought together neat or in the presenceof an inert solvent, particularly a hydrocarbon solvent. The inerthydrocarbon solvent may be aliphatic or aromatic. Also, aliphaticalcohols may be used by themselves or in combination with anothersolvent, when capable of dissolving the reactants.

The reaction may be carried out at room temperature (20° C.), butelevated temperatures are preferred. Usually, the temperature will be inthe range of from about 1000° to 225° C. Depending on the temperature ofthe reaction, the particular halogen used, the mole ratios and theparticular amine, as well as the reactant concentrations, the time mayvary from 1 to 24 hours, more usually from about 3 to 20 hours. Timesgreatly in excess of 24 hours do not particularly enhance the yield andmay lead to undesirable degradation. It is therefore preferred to limitthe reaction time to fewer than 24 hours.

The mole ratio of halohydrocarbon to amine compound will generally be inthe range from about 0.2 to 10 moles of amine compound per mole ofhalohydrocarbon, more usually 0.5 to 5 moles of amine compound per moleof halohydrocarbon. The mole ratio will depend upon the amount ofhalogen present in the halohydrocarbon, the particular halogen and thedesired ratio of hydrocarbon to amine compound.

Small amounts of residual halogen in the final composition are notdeleterious. Generally, the residual halogen, as bound halogen, will bein the range of 0 to 10 weight percent of the composition. Small amountsof halogen may be present as the hydrohalide salt of the hydrocarbonsubstituted alkylene polyamines.

Generally, the hydrocarbons used will have aliphatic unsaturation. Inparticular instances, the amines may react in a way resulting in theelimination of hydrogen halide, introducing further aliphaticunsaturation into the hydrocarbon radical. Therefore, the hydrocarbonradicals usually will be olefinically unsaturated. However, the olefinicunsaturation does not significantly affect the utility of the product,and when available, saturated aliphatic halide may be used.

After the reaction has been carried out for a sufficient length of time,the reaction mixture may be extracted with a hydrocarbon medium to freethe product from any low molecular weight amine salt which has formed.The product may then be isolated by evaporation of the solvent. Furtherseparation from unreacted hydrocarbon or purification may be carried outas desired, e.g., chromatography. (C) Another class of long chainhydrocarbyl reactants to form the improved dispersants of this inventionare any of the long chain hydrocarbyl-substituted hydroxy aromaticcompounds which are known in the art as useful for forming Mannichcondensation products. Such Mannich condensation products generally areprepared by condensing about 1 mole of a high molecular weighthydrocarbyl substituted hydroxy aromatic compound (e.g., having a numberaverage molecular weight of 700 or greater) with about 1 to 2.5 moles ofan aldehyde such as formaldehyde or paraformaldehyde and about 0.5 to 2moles of the second adduct, using the condensation conditions asdisclosed, e.g., in U.S. Pat. Nos. 3,442,808; 3,649,229; and 3,798,165(the disclosures which are hereby incorporated by reference in theirentirety). Such Mannich condensation products may include a long chain,high molecular weight hydrocarbon on the phenol group or may be reactedwith a compound containing such a hydrocarbon, e.g., polyalkenylsuccinic anhydride as shown in said aforementioned U.S. Pat. No.3,442,808.

The optionally substituted hydroxy aromatic compounds used in thepreparation of the Mannich base products include those compounds havingthe formula

    R.sup.1.sub.y.sbsb.1 --Ar--(OH).sub.z.sbsb.1

wherein Ar represents ##STR5## wherein q is 1 or 2, R¹ is a long chainhydrocarbon, R² is a hydrocarbon or substituted hydrocarbon radicalhaving from 1 to about 3 carbon atoms or a halogen radical such as thebromide or chloride radical, y₁ is an integer from 1 to 2, x₁ is aninteger from 0 to 2, and z₁, is an integer from 1 to 2.

Illustrative of such Ar groups are phenylene, biphenylene, naphthyleneand the like.

The long chain hydrocarbon R¹ substituents are olefin polymers asdescribed above for those olefin polymers useful informing reactants.

Representative hydrocarbyl substituted hydroxy aromatic compoundscontemplated for use in the present invention include, but are notlimited to, 2-polypropylene phenol, 3-polypropylene phenol,4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol,4-polyisobutylene phenol, 4-polyisobutylene-2-chlorophenol,4-polyisobutylene-2-methylphenol, and the like.

Suitable hydrocarbyl-substitued polyhydroxy aromatic compounds includethe polyolefin catechols, the polyolefin resorcinols, and the polyolefinhydroquinones, e.g., 4-polyisobutylene-1,2-dihydroxybenzene,3-polypropylene-1,2-dihydroxybenzene,5-polyisobutylene-1,3-dihydroxybenzene,4-polyamylene-1,3-dihydroxybenzene, and the like.

Suitable hydrocarbyl-substituted naphthols include1-polyisobutylene-5-hydroxynaphthalene,1-polypropylene-3-hydroxynaphthalene and the like.

(D) Still another class of long chain hydrocarbyl reactants to form theimproved dispersants of this invention are the Mannich baseaminophenol-type condensation products as they are known in the art.Such Mannich condensation products generally are prepared by reactingabout 1 mole of long chain hydrocarbon substituted mono and dicarboxylicacids or their anhydrides (e.g., polyisobutylene-substituted succinicanhydride) with an about 1 mole of amine-substituted hydroxy aromaticcompound (e.g., aminophenol), which aromatic compound can also behalogen- or hydrocarbyl-substituted, to form a long chain hydrocarbonsubstituted amide or imide-containing phenol intermediate adduct(generally having a number average molecular weight of 700 or greater),and condensing about a molar proportion of the long chain hydrocarbonsubstituted amide- or imide-containing phenol intermediate adduct withabout 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of thesecond adduct of this invention.

Suitable aminophenols include 2-aminophenol, 3-aminophenol,4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol,4-amino-2-bromophenol and 4-amino-3-ethylphenol.

The preparation and use of the hydroxy aromatic compounds andamino-substituted hydroxy aromatic compounds, and methods useful forreaction thereof with an aldehyde and the selected amine compound ofthis invention are as described in U.S. Pat. Nos. 4,820,432 and4,828,742, the disclosures of which are hereby incorporated herein intheir entirety.

As with the adducts formed from reaction of an amine and long chainhydrocarbyl reactant A, the adducts formed by reaction of amines andlong chain hydrocarbyl reactants B, C and D will preferably have withintheir structure, on average, at least about 0.5 (e.g., from about 0.5 to20), and preferably at about 1 (e.g., from about 1 to 15) reactive aminegroups per molecule.

PREPARATION OF THE N-CONTAINING POLYMER ADDUCT

Preparation of N-containing polymer adducts useful in the presentinvention can be illustrated as follows:

EXAMPLE A PIB-Cl

Into a reaction flask is introduced 950 g. of polyisobutylene(approximate number average molecular weight=950) dissolved in 1,000 ml.of carbon tetrachloride. The mixture is stirred and chlorine isintroduced at a rate of 235-250 ml. per minute, the temperature beingmaintained at 0° C. After the reaction mixture has taken up 51 g. ofchlorine, the introduction of chlorine is terminated, the carbontetrachloride is removed in vacuo and the chlorinated polyisobutyleneisolated and analyzed. Analysis: wt. percent chlorine, 7.0.

EXAMPLE B PIB-Succinimide

Into a reaction flask is introduced 225 g. of N-bromo-succinimide, 750g. of polyisobutylene (approximately 930 number average molecularweight) and 750 ml. of carbon tetrachloride, the flask swept withnitrogen and the solution heated to 70° C. while maintaining a positivenitrogen pressure on the flask. To the solution is then added dropwise0.5 g. of benzoyl peroxide in 50 ml. of carbon tetrachloride. At the endof the addition, the solution is cooled and the succinimide filteredoff. The carbon tetrachloride is removed in vacuo. Analysis: wt. percentbromine, 8.86.

EXAMPLE C PIB-EDA

Into a reaction flask is charged 1,156 g. of chloropolyisobutylene ofapproximately 950 number average molecular weight chlorinated to 7.8weight percent chlorine), 75 ml. of xylene and 330 ml. of ethylenediamine, followed by the addition of 330 ml. of n-butanol. The mixtureis then raised to a temperature of 100° C. over one hour and thetemperature is then raised to about 160° C. and maintained there forabout 41/2 hours. About 330 ml. of distillate is obtained while raisingthe temperature from 130° to 160° C. The reaction mixture is transferredto a separatory funnel with the aid of one liter of benzene, and themixture is washed repeatedly first with a dilute aqueous solution ofisopropyl alcohol, then with a dilute aqueous solution of a combinationof isopropyl alcohol and butanol and finally with water. The volatilematerials are then removed from a sample of the washed product bysparging with nitrogen to constant weight on a steam plate. Analysis:titrimetric equivalent wt., 806, equal to 1.74% N; wt. percent chlorine,0.62.

1,434 g. or about half of the volatile solvents is removed from the mainportion of the washed product. This solution containing about 25%volatile solvent (titrimetric equivalent weight=1,051) combined with 240g. of a mixture of other materials prepared similarly to provide a finalproduct having a titrimetric equivalent weight of 985, the product beingpolyisobutenyl ethylene diamine.

EXAMPLE D PIB-EDA

Into a reaction flask is introduced 1,000 g. of chloropolyisobutene(polyisobutene of approximately 420 number average molecular weightchlorinated to approximately 8 weight percent chlorine), 270 ml. ofethylene diamine and 270 ml. of n-butanol. The mixture is heatedgradually to 1700° C. during 11/2 hours; distillate is collected mainlybetween 130° C. and 1600° C. The mixture is then heated for about 3hours at 170° C. At the end of this time, 1,000 ml. of toluene and 250ml. of methyl isobutyl carbonol are added and the mixture washed withdilute aqueous isopropyl alcohol followed by repeated washings withwater. Some of the volatile solvents are then removed on a steam bathusing a nitrogen stream. The combined products from two similar runs arethen filtered, yielding 3,911 g. Analysis: titrimetric equivalent wt.,840, equal to 1.67 wt. percent N. Complete removal of volatile solventsfrom a small sample indicate the product contains about 40% solvents,i.e., toluene and methyl isobutyl carbinol.

EXAMPLE E PIB-EDA

Following the procedure of Example D, 1,000 g. of chloropolypropylene(polypropylene of about number average 800 molecular weight chlorinatedto about 6 weight percent chlorine) is reacted with 270 g. of ethylenediamine. The product as finished contains about 15% volatile solvents.Analysis: titrimetric equivalent wt., 1,080, equal to 1.3 wt. percent N.

EXAMPLE F PIB-TEPA

Into a reaction flask is introduced 1,500 g. of chloropolyisobutylene(polyisobutylene of approximately 950 molecular weight chlorinated to5.6 weight percent chlorine), 285 g. of alkylene polyamine having anaverage composition of tetraethylene pentamine and 1,200 ml. of benzene,the mixture is heated to reflux, followed by stripping off the benzeneand heating the mixture at about 170° C. for about 4 hours. The mixtureis then allowed to cool, diluted with equal volumes of mixed hexanes andabsolute ethanol, heated to reflux and 1/3 volume of 10 weight percentaqueous sodium carbonate added. The phases are separated, and theorganic phase is washed with water, followed by removing the volatilematerials in vacuo. Analysis: wt. percent N, 4.15; molecular weight(ThermoNam), 1,539.

EXAMPLE G PIB-EDA

Following the procedure of Example D, 950 g. of chloropolyisobutylene(polyisobutylene of approximately 950 M_(n) chlorinated to 4.48 weightpercent chlorine) is combined with 270 ml. of ethylene diamine (EDA) in270 ml. of n-butanol. The product as finished contains about 20 percentvolatile solvents. Analysis: titrimetric equivalent wt., 976, equal to1.44 wt. percent N.

EXAMPLE H PIB-NH₂

Into a high pressure bomb is introduced 1,200 g. of polyisobutenylchloride (polyisobutylene of approximately 500 M_(n) chlorinated to 8wt. percent chlorine) and 400 g. of liquid ammonia, the bomb sealed andheated at 1500° C. with rocking for about 15 hours. After cooling, thepressure is vented and the reaction mixture taken up in mixed hexanes,water and alcohol. The organic phase is then washed with 500 ml. of 5percent sodium hydroxide, followed by repeated washings with water. Thesolvents are then distilled off and the residue, which weighed 767 g.,is filtered through Celite to recover the PIB-NH₂.

EXAMPLE I PIBSA-Amino Phenol-TEPA Mannich Base

(a) A polyisobutenyl succinic anhydride having a SA:PIB ratio of 1.13 isprepared by heating a mixture of 100 parts of polyisobutylene (2225M_(n) ; M_(w) /M_(n) =2.5) with 6.14 parts of maleic anhydride to atemperature of about 220° C. When the temperature reaches 120° C., thechlorine addition is begun and 5.07 parts of chlorine at a constant rateare added to the hot mixture for about 5.5 hours. The reaction mixtureis then heated at 220° C. for about 1.5 hours and then stripped withnitrogen for about one hour. The resulting polyisobutenyl succinicanhydride has an ASTM Saponification Number of 54. The PIBSA product is80 wt. % active ingredient (A.I.), the remainder being primarilyunreacted PIB.

(b) A mixture containing 104 g. (0.05 mole) of the polyisobutylenepolymer substituted succinic anhydride material so prepared, 5.45 g.(0.05 mole) of 4-aminophenol and 67 g. of S15ON lubricating oil isstirred and slowly heated to 160° C. while under a nitrogen blanket. Thereaction mixture is then heated at 160° C. for 3 hours and filtered. Theresulting oil solution of polyisobutylene polymer substitutedN-(hydroxyphenyl) succinimide analyzes for 0.22 wt % N.

(c) About 59.6 g. (0.014 mole) of the N-(hydroxyphenyl) polyisobutylenepolymer substituted succinimide solution so prepared is mixed with 2.0g. (0.0125 equivalent of primary N) of tetraethylene pentaamine (TEPA),0.46 g. (0.015 mole) of formaldehyde, and 2.5 g. of S150N and reacted at80° C. for one hour under nitrogen atmosphere. The reaction mixture isthen heated to 160° C. for one hour and stripped at 160° C. for anotherhour with nitrogen gas. The reaction product analyzes for 1.28 wt % N.

EXAMPLE J

A portion of the dispersant of Example I is reacted with boric acid toprovide a S15ON solution containing a borated polyisobutenyl succinimidehaving a nitrogen content of about 1.28 wt. %, a boron content of 0.23wt. % (50% a.i.) and 50 wt. % of unreacted PIB and mineral oil (S150N).

EXAMPLE K PIBSA-Amino Phenol-TEPA Mannich Base

(a) A polyisobutenyl succinic anhydride (PIBSA) having a SA:PIB ratio of1.24, is prepared by heating a mixture of 100 parts of polyisobutylene(1320 M_(n) ; M_(w) /M_(n) =2.5) with 11 parts of maleic anhydride to atemperature of about 220° C. When the temperature reaches 120° C., thechlorine addition is begun and 10 parts of chlorine at a constant rateare added to the hot mixture for about 5 hours. The reaction mixture isthen heated at 220° C. for about 1.5 hours and then stripped withnitrogen for about one hour. The resulting polyisobutenyl succinicanhydride was diluted with S150N mineral oil to obtain a product havingan ASTM Saponification Number of 69. The PIBSA product is 59 wt. %active ingredient (A.I.), the remainder being primarily unreacted PIBand mineral oil.

(b) A mixture containing 104 g. (0.05 mole) of the polyisobutylenepolymer substituted succinic anhydride material so prepared, 5.45 g.(0.05 mole) of 4-aminophenol and 67 g. of S150N lubricating oil isstirred and slowly heated to 160° C. while under a nitrogen blanket. Thereaction mixture is then heated at 160° C. for 3 hours and filtered. Theresulting oil solution of polyisobutylene polymer substitutedN-(hydroxyphenyl) succinimide analyzes for 0.22 wt % N.

(c) About 59.6 g. (0.025) of the N-(hydroxyphenyl) polyisobutylenepolymer substituted succinimide solution so prepared is mixed with 2.4g. (0.0125 equivalent of primary N) of tetraethylene pentaamine (TEPA),0.42 g. (0.014 mole) of formaldehyde, and 2.5 g. of S150N and reacted at80° C. for one hour under nitrogen atmosphere. The reaction mixture isthen heated to 160° C. for one hour and stripped at 160° C. for anotherhour with nitrogen gas. The reaction product analyzes for 1.52 wt % N.

EXAMPLE L PIB-Phenol-TEPA Mannich Base

(a) About 50 g. of polyisobutylene (2225 M_(n) ; M_(w) /M_(n) =2.5) isdissolved in 100 ml of chlorobenzene and added to a solution containing10.45 g. of phenol in 300 ml of chlorobenzene. While stirring at roomtemperature under a nitrogen blanket, 0.5 g. of BF₃ gas was bubbled intothe charged solution, and the reaction mixture was stirred while thetemperature was increased to 50° C. for about 1 hour. The reactionmixture is then neutralized with gaseous ammonia until a neutral pH wasobtained. The solution is filtered and the filtrate is heated to 150° C.to distill of the solvent and excess phenol. Analytical results showed70% conversion to the desired polyisobutylene-substituted phenol.

(b) 25 Grams of the alkylated phenol so prepared is dissolved in 25 g.of S150N lubricating oil. To the solution is added 1.1 g. of TEPA and0.35 g. of formaldehyde at 30° C. under N₂. The mixture is heated to115° C. and kept at that temperature for 1 hour in a four necked roundbottomed 500 mol flask. Then, the reaction mixture's temperature israised to 130° C. while the reaction vessel was swept with dry N₂ gasfor 45 minutes. The stripped reaction mixture was then cooled to roomtemperature, diluted with 100 ml. of heptane, and filtered. The filtratewas then stripped at 130° C. with dry N₂ gas to remove heptane.

EXAMPLE M

(a) A polyisobutenyl succinic anhydride having a succinic anhydride (SA)to polyisobutenylene mole ratio (i.e., a SA:PIB ratio) of 1.04 isprepared by heating a mixture of 100 parts of polyisobutylene (940 M_(n); M_(w) /M_(n) approximately equal to 2.5) with 13 parts of maleicanhydride to a temperature of about 220° C. When the temperature reaches120° C., the chlorine addition is begun and 10.5 parts of chlorine at aconstant rate are added to the hot mixture for about 5.5 hours. Thereaction mixture is then heated at 220° C. for about 1.5 hours and thenstripped with nitrogen for about one hour. The resulting polyisobutenylsuccinic anhydride has an ASTM Saponification Number of 112. The PIBSAproduct is 90 wt. % active ingredient (A.I.), the remainder beingprimarily unreacted PIB.

(b) A mixture of 200 parts by weight of the PIBSA product formed inExample M(a) and 188 parts of S150 mineral oil is heated to 150° C.under N₂. Then 32.3 parts of amido-amine I were added dropwise whilestirring and light nitrogen sparging. The mixture is nitrogen strippedat 150° C. for 3 hours and then filtered. The oil solution is found tohave the nitrogen content of 2.37 wt. % and a kinematic viscosity of107.4 cSt at 100° C.

(c) A mixture of 200 parts by weight of the PIBSA product formed inExample M(a) and 174.5 parts of S150 mineral oil is heated to 150° C.under N₂. Then 17.9 parts of tetraethylenepentaamine are added dropwisewhile stirring and light nitrogen sparging. The mixture is nitrogenstripped at 150° C. for 3 hours and then filtered. The oil solution isfound to have the nitrogen content of 1.72 wt. % and a kinematicviscosity of 156.3 cSt at 100° C.

EXAMPLE N

A mixture of 200 parts by weight of the PIBSA product formed as inExample K(a) and 42 parts of S150 mineral oil is heated to 150° C. underN₂. Then 11.6 parts of tetraethylenepentaamine are added dropwise whilestirring and light nitrogen sparging. The mixture is nitrogen strippedat 150° C. for 3 hours and then filtered. The oil solution is found tohave the nitrogen content of 1.65 wt. % and a kinematic viscosity of213.0 cSt at 100° C.

EXAMPLE O

A mixture of 200 parts by weight of the PIBSA product formed in ExampleI(a) and 119 parts of S150 mineral oil is heated to 150° C. under N₂.Then 8.8 parts of tetraethylenepentaamine are added dropwise whilestirring and light nitrogen sparging. The mixture is nitrogen strippedat 150° C. for 3 hours and then filtered. The oil solution is found tohave the nitrogen content of 1.05 wt. % and a kinematic viscosity of487.8 cSt at 100° C.

EXAMPLE P

(A) A polyisobutenyl propionic acid (PIBA) having a functionality of1.09 is prepared by heating a mixture of 2,000 parts of polyisobutylene(2225 M_(n) ; M_(w) /M_(n) ˜2.5) while bubbling 120 g of chlorine gasfor a period of 10 hours at 130°-140° C. The chlorinated PIB analyzedfor 2.8 wt. % chlorine. To the chlorinated PIB at 120° C., 149.6 g ofacrylic acid are added and the reaction mixture is slowly heated to 230°C. at a rate of 15°-20° C./hour while under nitrogen blanket. Thereafterthe reaction product is soaked at 230° C. for two hours and nitrogenstripped at 230° C. for one hour. The filtered product analyzed for atotal acid number (ASTM D-94) of 26.2 and 70.3% active ingredient; theremaining being primarily unfunctionalized PIB.

(b) A mixture of 107 parts by weight of the PIBA product formed inExample (a) and 47 parts of S150 mineral oil is heated to 160° C. underN₂. Then 4.73 parts of tetraethylenepentaamine are added dropwise whilestirring and light nitrogen sparging. The mixture is nitrogen strippedat 150° C. for 3 hours and then filtered. The oil solution is found tohave the nitrogen content of 1.03 wt %.

EXAMPLE Q

Using the procedure of Example P(b), a mixture of 107 parts by weight ofthe PIBA product formed in Example P(a) and 47.3 parts of S150 mineraloil is heated to 160° C. under N₂. Then 4.8 parts of a commercialpolyethylenepolyamine (PAM containing an average of 12 carbon atoms and6 nitrogen atoms per molecule), are added dropwise while stirring andlight nitrogen sparging. The mixture is nitrogen stripped at 160° C. for3 hours and then filtered. The oil solution is found to have thenitrogen content of 0.98 wt %.

EXAMPLE R

1.80 mole of polyisobutylene succinic anhydride (Sap. No. 48, 86 wt. %active ingredient) is prepared from 22225: M_(n) PIB via a simultaneousprocess with chlorine gas and maleic anhydride was charged into areaction vessel with 2897 g. of mineral oil S15ON and heated to 150° C.under nitrogen blanket. Thereafter, one mole of polyalkylene polyamine(as used in Example Q) is added to the reaction solution while nitrogensparging for a period of one hour. After the addition is completed, thereaction mixture is nitrogen stripped at 150° C. for two hours andfiltered. The product, a 52 wt. % oil solution of polyisobutenylsuccinimide, analyzes for 0.88 wt. % nitrogen (of which 47 wt. % issecondary amino groups).

AROMATIC NITROGEN-CONTAINING MONOMER

The aromatic nitrogen-containing monomers (also referred to herein as"aromatic N-monomers") employed in the present invention contain one ormore aromatic ring, wherein at least one aromatic ring is substituted bya --NH(R^(a)) group, wherein R^(a) is hydrogen or hydrocarbyl (e.g., C₁to C₂₅ hydrocarbyl, and preferably H or C₁ to C₃ alkyl). Such aromaticN-monomers include compounds of the formula: ##STR6## wherein Ar is asubstituted or unsubstituted aromatic radical, R^(a) is as defined aboveand y is an integer of at least 1 (e.g., 1 to 4, preferably 1-2).

The Ar radical will generally contain from 6 to 20 ring carbon atoms andcan comprise a single aromatic ring, fused aromatic rings, or linkedaromatic rings, and can be substituted or unsubstituted. Preferably, thesubstituents on the Ar radical are positioned ortho- and/or meta- to theN substituent. The Ar radical's substituents can be the same ordifferent and can comprise --Z² or --Z¹ Z² wherein Z¹ is a memberselected from the group consisting of (a) a branched or straight chainalkylene group (e.g., --C_(n) H_(2n) --, wherein n is an integer of from1 to 20, preferably from 1 to 6) which can contain one or more --O-- or--S-- chain atoms (e.g., --(C_(n') H_(2n') X)_(n") -- wherein n' is aninteger of from 1 to 6, preferably from 1 to 4, and n" is an integer offrom 1 to 20, preferably from 1 to 6 and X is O or S), and (b) groups ofthe formula: ##STR7## wherein n₃ is from 1 to 4 (and preferably 1 to 2),R^(c) in each instance in which it appears is independently C₁ to C₁₂alkyl (preferably C₁ to C₄ alkyl), D in each instance in which itappears is independently Cl, Br or I, y" is an integer of from 0 to 4(preferably from 0 to 3), y'" is an integer of from 0 to 4 (preferablyfrom 0 to 3), and wherein R^(b) is H or C₁ to C₂₀ alkyl and y' is aninteger of from 1 to 4 (preferably 1 or 2), with the proviso that thesum of y'+y"+y'" is from 1 to 5 (preferably from 1 to 4, more preferablyfrom 1 to 3), and wherein Z² is a member selected from the groupconsisting of H, --OH, --halide, --R^(c), --SO₃ H, --PO₃ H, --SO₃ R^(c),--PO₃ R^(c), --CO₂ R^(c), --CO₂ H, or --NO₂, wherein R^(c) ishydrocarbyl (e.g., C₁ to C₁₂ hydrocarbyl). The Ar group, if substituted,will preferably be substituted by 1 to 3, more preferably 1 to 2, C₁ toC₂₀ hydrocarbyl (e.g., alkyl) groups, or with 1 to 3 halogen radicals(e.g., Cl--, Br--, or I--). Examples of suitable unsubstituted Ar groupsare phenyl, naphthyl, bi-phenyl, terphenyl, quarterphenyl,quinquiphenyl, sexiphenyl, naphthylphenyl, phenylnaphthyl and the like.Examples of fused aromatic ring Ar systems are anthracene, phenanthrene,tetracene, acenaphthene and phenalene. Preferred polyaromatics are thepolyphenylenes.

To avoid competing side reactions R^(a) and R^(c) are preferablysubstantially free of polymerizable ethylenically unsaturated doublebonds.

Preferred aromatic N-monomers for use in the present invention comprisecompounds of the formula:

    Ar' NH(R.sup.b)!.sub.y'

wherein Ar' is ##STR8## wherein Z¹ is as defined above, R^(c) in eachinstance in which it appears is independently C₁ to C₁₂ alkyl(preferably C₁ to C₄ alkyl), D in each instance in which it appears isindependently Cl, Br or I, y" is an integer of from 0 to 4 (preferablyfrom 0 to 3), y'" is an integer of from 0 to 4 (preferably from 0 to 3),and wherein R^(b) is H or C₁ to C₂₀ alkyl and y' is an integer of from 1to 4 (preferably 1 or 2), with the proviso that the sum of y'+y"+y'" isfrom 1 to 5 (preferably from 1 to 4, more preferably from 1 to 3).

Illustrative of aromatic N-monomers useful in this invention areaniline, N-methyl aniline, N-ethyl aniline, N-propyl aniline,N-isopropyl aniline, N-(tert-butyl) aniline, 2-aminophenol,3-aminophenol, 2-amino-4-chloro-6-nitrophenol, 2-amino-4,6-dichlorophenol, 2-amino-4,6-dinitrophenol, 2-amino-4-chlorophenol,2-amino-4-nitrophenol, 2-amino-1-phenol-4-sulfonamide;3-amino-2-hydroxybenzoic acid, 2-amino-6-nitro-4-methylyphenol,6-amino-4-nitro-2-methylphenol, 2-amino-3-nitro-4-methylphenol,2-amino-4-methylphenol, 2-amino-4-(methylsulfonyl)phenol,3'-amino-2'-hydroxy-5'-nitroacetanilide,3'-amino-4'-hydroxy-5'-nitroacetanilide, diphenyl amine, 0-toluidine,m-toluidine, 2,3-xylidine, 2,5-xylidine, 2,6-xylidine, 3,5-xylidine,o-anisidine, m-anisidine, o-phenetidine, p-cresidine, acetanilide,acetoacetanilide, o-chloroaniline, m-chloroaniline, 2,5-dichloroaniline,2-amino benzene sulfonic acid, 3-amino benzene sulfonic acid,o-nitroaniline, m-nitroaniline, naphthalene amines, such as:1-(naphthylene)amine, 2-(naphthylene)amine, and the like,N-phenyl-2-napththalene amine, 8-amino-1-naphthalene carboxylic acid,N-(monosubstituted) amino-phenols, such as 3-anilinophenol,3-ethylamino-4-methylphenol, 3-hydroxy-N-phenylaniline,3-hydroxy-2'-methyldiphenylamine, 3-ethylaminophenol, 3-methylamino-4-methylphenol, 3-ethylamino-4-methylphenol, 4-anilinophenol,4-acetaminophenol, 2-amino-3,6-dichloro-1-phenol-4-sulfonic acid,2-amino-6-chloro-1-phenol-4-sulfonic acid, 3-amino-1-phenol-4-sulfonicacid, 2-amino-1-phenol-4-sulfonic acid,5-amino-6-hydroxy-3-methylbenzenesulfonic acid,4-acetamido-6-amino-l-phenol-2-sulfonic acid,5-amino-1-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid,8-amino-2-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid,2-amino-1-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid,7-amino-2-naphthalenesulfonic acid, 7-amino-1-naphthalenesulfonic acid,1-amino-2,7-naphthalenedisulfonic acid, 4-amino-2,7-naphthalenesulfonicacid, 4-amino-2,6-naphthalenedisulfonic acid,8-amino-1,6-naphthalenedisulfonic acid,5-amino-1,3-naphthalenedisulfonic acid,3-amino-1,5-naphthalenedisulfonic acid, 5-amino-1-naphthalenol,7-amino-2-naphthalenol, 4-hydroxy-8-amino-2-naphthalenesulfonic acid,4-hydroxy-7-amino-2-naphthalenesulfonic acid,4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, aniline HCl , anilinesulfate, and the like.

Preferred aromatic N-monomers are o-methylaniline, o-ethylaniline,o-methoxyaniline, o-phenylaniline, o-aminoaniline, o-fluroaniline,o-chloroaniline, o-nitroaniline, o-methylaniline, m-ethylaniline,m-methoxyaniline, m-chloroaniline, m-nitroaniline, p-phenylaniline,N-methylaniline, N-ethylaniline, N-benzylaniline, N-methylaniline,N-phenylaniline, and N-naphthylaniline, and mixtures thereof.

Most preferred aromatic N-monomers on the present invention are aniline,o-toluidine, m-toluidine, m-ethylaniline, and o-ethylaniline.

Grafting of Aromatic N-Monomer

The amino-substituted polymer is grafted with aromatic N-monomer inaccordance with this invention by contacting the aromatic N-monomer andamino-substituted polymer under polymerizing conditions in apolymerization zone in the presence of an effective amount of anoxidizing agent.

Oxidizing agents which can be employed have a reducing single electronpotential (E°_(red)) greater than 1.00 volt, preferably grater than 1.5volts and more preferably greater than 1.7 volts (e.g., from 1.5 to2.5). E°_(red) values for standard half reactions are obtained fromLange's Handbook of Chemistry, 13th ed., page 6-2 to 6-5, (J. A. Dean,Ed., McGraw Hill Book Company (1985), which is incorporated herein byreference.

Examples of suitable oxidizing agents include chemical compounds whichcontain a metal ion which can change its valence, and also includenon-metallic compounds. Examples are ammonium peroxydisulfate (NH₄)₂ S₂O₈ !, potassium iodate (KIO₃), iron (III) chloride (FeCl₃), sodiumpersulfate Na₂ S₂ O₈ !, potassium persulfate K₂ S₂ O₈ !, potassiumdichromate (K₂ Cr₂ O₇), hydrogen peroxide (H₂ O₂) (e.g., 30% solution inwater), chromium trioxide CrO₃ !, sodium chlorate Na₂ ClO₃ !, ammoniumdichromate (NH₄) ₂ Cr₂ O 7!, (NH₄) ₂ Ce (NO₃) ₆, Ce(SO₄)₂, and the like.

The oxidizing agents can be dissolved in polar organic or inorganicsolvents which are inert towards the particular oxidants used. Typicalsolvents are water, alcohols, acetonitrile, acetic acid, acetone,amides, ethers and the like. Typical concentrations for the oxidant arewithin the range 0.1-1.0 molar.

In practicing the instant invention, auxiliary acids including, but notlimited to, mineral, carboxylic and sulfonic may be used in conjunctionwith the aforementioned inorganic or organic oxidants. Thus, acids suchas sulfuric, hydrochloric, acetic, trifluoroacetic, methanesulfonic ortrifluoromethanesulfonic can be employed. Such acid may be co-dissolvedwith the oxidant in a suitable solvent used as a solvent for theoxidant. Such added acids may be preferred but are not necessary inconjunction with the preferred oxidants. When auxiliary acids are addedto the system, they are added in amounts in the range 0.01 to 100 molesacid/mole oxidant.

The oxidizing agent is generally employed in an amount of from 0.01 to 3mole (and preferably from 0.2 to 1 mole) per mole of the aromaticN-monomer.

The conditions of temperature and pressure under which thepolymerization is performed can vary widely, and generally temperaturesof from about -20° to 100° C., preferably from about 0° to 30° C., willbe employed. Temperatures of greater than 100° C. can be employed butcan cause excessive thermal decomposition of the product and increasedby-products (including homopolymer of the aromatic N-monomer, e.g.,polyaniline homopolymer from aniline). Similarly, temperatures of lessthen -20° C. can be used, but uneconomically slow reaction rates canresult. The pressure is preferably selected to maintain the polymer andmonomer feed in substantially liquid form in the polymerization zone,and generally pressures from about 0.1 to 1000 kPa, and preferably fromabout 1 to 100 kPa, will be employed. As the polymerization reaction isslightly exothermic, the polymerization zone will be generally providedwith a cooling means, which can comprise any of the conventionally useddevices for cooling liquid media (e.g., external or internal reactorcooling coils, feedstream indirect heat exchanger(s), reaction liquidrecycle through a pump around heat exchanger, introduction of a quenchfluid (e.g., a cooled solvent or gas), and the like). Cooling of thepolymerization reaction liquid can also be effected by evaporativecooling, as by continuously, or intermittently, introducing alow-boiling solvent which is evaporated from the surface of the reactionliquid.

The polymerization reaction time can vary widely, depending on suchfactors as the size of the reactor, the type, amounts and notes of thefeedstreams charged, the temperatures employed, and other factors.Generally, however, the polymerization will be conducted for a time offrom about 0.1 to 24 hours, preferably from about 1 to 15 hours and morepreferably from about 2 to 6 hours.

The grafting polymerization reaction is believed to be an oxidationreaction, and therefore, the reactants are preferably charged in thesubstantial absence of reducing agents such as hydroquinone, NH4OH,hydrazine, and the like, as these materials may impede the desiredgrafting reaction.

The polymerization can be effected in the presence or absence of asolvent. For example, suitable solvents include hydrocarbon solventssuch as aliphatics, cycloaliphatics, and aromatic hydrocarbon solvents,or halogenated versions of such solvents. Preferred are C₁₂ or lowerstraight-chain or branched-chain, saturated hydrocarbons, and C₅ to C₉saturated alicyclic or aromatic hydrocarbons, or C₂ to C₆ halogenatedhydrocarbons. Examples of such solvents are hexane, butane, pentane,heptane, cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane,methyl cyclohexane, isooctane, benzene, toluene, xylene, chloroform,chlorobenzene, tetrachloroethylene, dichloroethane and trichloroethane.

Generally, from 0.01 to 500 moles, preferably from about 0.1 to 200moles, and more preferably from 0.1 to 100 moles, of aromatic N-monomerare charged to the polymerization zone per molar equivalent of reactiveamine of the long chain hydrocarbon-substituted reactant charged. Thenumber of molar equivalents of reactive amine is equal to the moles oflong chain hydrocarbon-substituted reactant charged multiplied by theaverage number of reactive amine groups (i.e., primary or secondaryamine groups) per molecule of the long chain hydrocarbon-substitutedreactant. For example, in an interpolymer containing an average of 0.8reactive amine groups per polymer molecule, for the purposes of theabove charge ratios, one mole of the long chain hydrocarbon-substitutedreactant contains 0.8 molar equivalents of reactive amino groups.

The concentration of aromatic-N-monomer units produced in the productpolymer can vary widely. For lubricating oil additives, the graftedpolymer will preferably contain from about 0.5 to 30 wt. %, and morepreferably from about 1 to 10 wt. % monomer units derived from thearomatic N-monomer (e.g., aniline), and for electronic applications, thegrafted polymer will preferably contain from about 20 to 80 wt. %,preferably 30 to 50 wt. % of monomer units derived from thearomatic-N-monomer (e.g., aniline).

The polymerization grafting reaction can be effected in a continuous,semi-continuous or batchwise manner, and can be carried out in anyconventional reactor, such as in one or more stirred tank reactor,tubular reactor, and the like.

In the grafting process, the long chain hydrocarbon-substituted reactantand aromatic N-monomer are contacted with the acidic oxidizing solution.Under these conditions, the long chain hydrocarbon-substituted reactantis unable to homopolymerize as it lacks the polymerizable group. Thearomatic N-monomer, however, readily polymerizes under these reactionconditions. The slow addition of the long chain hydrocarbon-substitutedreactant already mixed with acidic oxiding solution or the slow additionof the aromatic N-monomer mixed with long chain hydrocarbon-substitutedreactant to the acidic oxiding solution is essential for the preventionof significant homopolymerization of aromatic N-monomer.

The grafting reaction of long chain hydrocarbon-substituted reactantswith aromatic N-monomers in accordance with this invention can beillustrated by the grafting of aniline onto apolyisobutylene-substituted amine (PIB-NH₂). Attempts to establish theexact structure of polyaniline have been difficult. The redox chemistryof polyaniline is complicated by the large number of possible chemicalstructures for the polyaniline in an idealized structure, the polymer'sgraft segment units formed in this invention can be written as follows:##STR9## where x is a number of from 1 to 100,000, preferably from 2 to1,000, and wherein PIB represents the balance of the polymer, which cancontain an average of one or more such graft segments per polymer chain.However, under the preparation conditions of this invention, thestructure of the grafted polyaniline polymer units can also berepresented as follows: ##STR10##

The above structure can also be seen as the polysemiquinone radicalcation form: ##STR11## wherein A is an anion (e.g., chloride anion), xis as defined above, and y is 0.5 which polymer form will be hereincalled an emeraldine salt. The polymer can be reacted with 0.1M ammoniumhydroxide to get polyaniline in the emeraldine base form.

The emeraldine base form of the grafted polymer of the present inventionalternating reduced and oxidized repeat units can be presented asfollows: ##STR12## where again x and y are as defined above.

Furthermore, the repeating units can be protonated by Bronsted acid suchas aqueous HCl to produce or regenerate the corresponding salt as shownabove.

The grafted polymers prepared by the process of this invention aresoluble in common organic solvents (including non-polar organicsolvents) and in mineral oils, and possess electrically conductingproperties. The novel polymers of this invention are useful inoleaginous compositions as dispersant-viscosity index improveradditives, as dispersant additives, and possess antioxidant properties.The polymers of this invention are characterized by improvedthermooxidative and thermal stability properties compared to theamino-substituted polymers from which they are prepared.

The polymers of this invention also find utility in other applicationssuch as thermoplastic conductivity systems, soluble conductive systemscapable of being cast into coherent films, additives for conventionalthermoplastics, and the like. The novel polymers have high electricalconductivities, in general from 10 to 10⁻⁶ > ohm⁻¹ cm⁻¹, and goodmechanical properties. The electrical conductivity (in ohms⁻¹ cm⁻¹) isdetermined by applying conductive copper contacts to the film andcarrying out the measurement by the two-point method.

The polymers of this invention find utility in the construction oflight-weight rechargable storage batteries, electrochromic displaydevices, electo-optical switching and memory devices, neutron detectors,solar energy cells, ion exchangers, non-linear optic devices,molecule-based electronics, anti-static treatment of plastics andtextiles and semiconductor components. They constitute an advance in theart, especially where good mechanical properties of the components,coupled with low specific gravity and well-balanced properties, areimportant.

It is not essential to remove homopolymer from graft polymer forelectronic applications, but for lube additive applications homopolymer(if any is formed) could be removed by blending the grafted product withmineral oil (e.g. at temperatures of from about 80° C. to 100° C. forfrom about 4 to 8 hours) and then filtering this mixture to remove thehomopolymer which is insoluble in mineral oil.

OLEAGINOUS COMPOSITIONS

The dispersants of the present invention can be incorporated into alubricating oil (or a fuel in any convenient way. Thus, these mixturescan be added directly to the lubricating oil (or fuel) by dispersing ordissolving the same in the lubricating oil (or fuel) at the desiredlevel of concentration of the dispersant. Such blending into theadditional lubricating oil (or fuel) can occur at room temperature orelevated temperatures. Alternatively, the dispersants can be blendedwith a suitable oil-soluble solvent/diluent (such as benzene, xylene,toluene, lubricating base oils and petroleum distillates, including thevarious normally liquid fuels described in detail below) to form aconcentrate, and then blending the concentrate with a lubricating oil(or fuel) to obtain the final formulation. Such dispersant concentrateswill typically contain (on an active ingredient (A.I.) basis) from about3 to about 45 wt. %, and preferably from about 10 to about 35 wt. %,dispersant additive, and typically from about 30 to 90 wt. %, preferablyfrom about 40 to 60 wt. %, base oil, based on the concentrate weight.

The oil-soluble additives of the present invention possess very gooddispersant and antioxidant properties as measured herein in a widevariety of environments. Accordingly, the additives are used byincorporation and dissolution into an oleaginous material such as fuelsand lubricating oils. When the additives of this invention are used innormally liquid petroleum fuels such as middle distillates boiling fromabout 65° to 430° C., including kerosene, diesel fuels, home heatingfuel oil, jet fuels, etc., a concentration of the additives in the fuelin the range of typically from about 0.001 to about 0.5, and preferably0.005 to about 0.15 weight percent, based on the total weight of thecomposition, will usually be employed. The properties of such fuels arewell known as illustrated, for example, by ASTM Specifications D #396-73(Fuel Oils) and D #439-73 (Gasolines) available from the AmericanSociety for Testing Materials ("ASTM"), 1916 Race Street, Philadelphia,Pa. 19103. Normally liquid fuel compositions comprisingnon-hydrocarbonaceous materials such as alcohols, ethers, organo-nitrocompounds and the like (e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) are also within the scope of the invention.Such materials can be mixed with the hydrocarbon fuel in varying amountsof up to about 10-20% or more. For example, alcohols such as methanol,ethanol, propanol and butanol, and mixtures of such alcohols areincluded in commercial fuels in amounts of up to about 10%. Otherexamples of materials which can be mixed with the fuels include diethylether, methyl ethyl ether, methyl tertiary butyl ether, andnitromethane. Also within the scope of the invention are liquid fuelsderived from vegetable or mineral sources such as corn, alfalfa, shaleand coal. Normally liquid fuels which are mixtures of one or morehydrocarbonaceous fuels and one or more non-hydrocarbonaceous materialsare also contemplated.

The fuel compositions of this invention can contain, in addition to theproducts of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes, depositpreventers or modifiers such as triaryl phosphates, dyes, cetaneimprovers, antioxidants such as 2,6-ditertiary-butyl-4-methylphenol,rust inhibitors, bacteriostatic agents, gum inhibitors, metaldeactivators, upper cylinder lubricants and the like.

The additives of the present invention find their primary utility inlubricating oil compositions which employ a base oil in which theadditives are dissolved or dispersed. Such base oils may be natural orsynthetic. Base oils suitable for use in preparing the lubricating oilcompositions of the present invention include those conventionallyemployed as crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, marine and railroad diesel engines, and the like.Advantageous results are also achieved by employing the additives of thepresent invention in base oils conventionally employed in and/or adaptedfor use as power transmitting fluids, universal tractor fluids andhydraulic fluids, heavy duty hydraulic fluids, power steering fluids andthe like. Gear lubricants, industrial oils, pump oils and otherlubricating oil compositions can also benefit from the incorporationtherein of the additives of the present invention.

These lubricating oil formulations conventionally contain severaldifferent types of additives that will supply the characteristics thatare required in the formulations. Among these types of additives areincluded viscosity index improvers, antioxidants, corrosion inhibitors,detergents, dispersants (especially ashless dispersants such aspolyisobutylene succinimides and borated dreivatives thereof), pourpoint depressants, antiwear agents, friction modifiers, etc. asdescribed in U.S. Pat. No. 4,797,219, the disclosure of which is herebyincorporated by reference in its entirety. Some of these numerousadditives can provide a multiplicity of effects, e.g. adispersant-oxidation inhibitor. This approach is well known and need notbe further elaborated herein.

In the preparation of lubricating oil formulations it is common practiceto introduce the additives in the form of 10 to 80 wt. %, e.g., 20 to 80wt. % active ingredient concentrates in hydrocarbon oil, e.g. minerallubricating oil, or other suitable solvent. Usually these concentratesmay be diluted with 3 to 100, e.g., 5 to 40 parts by weight oflubricating oil, per part by weight of the additive package, in formingfinished lubricants, e.g. crankcase motor oils. The purpose ofconcentrates, of course, is to make the handling of the variousmaterials less difficult and awkward as well as to facilitate solutionor dispersion in the final blend. Thus, a dispersant would be usuallyemployed in the form of a 40 to 50 wt. % concentrate, for example, in alubricating oil fraction.

The additives of the present invention will be generally used inadmixture with a lube oil basestock, comprising an oil of lubricatingviscosity, including natural and synthetic lubricating oils and mixturesthereof.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methyl-poly isopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of poly-ethylene glycol having a molecularweight of 500-1000, diethyl ether of polypropylene glycol having amolecular weight of 1000-1500); and mono- and poly-carboxylic estersthereof, for example, the acetic acid esters, mixed C₃ -C₈ fatty acidesters and C₁₃ Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester formed by reacting one moleof sebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-ethylhexyl)silicate,tetra-(p-tertbutylphenyl)silicate, hexa-(4-methyl-2-pentoxy)disiloxane,poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other syntheticlubricating oils include liquid esters of phosphorus-containing acids(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester ofdecylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts effective to provide their normalattendant function. Representative effective amounts of such additives(as the respective active ingredients) in the fully formulated oil areillustrated as follows:

    ______________________________________                                                         Wt. % A.I.                                                                              Wt. % A.I.                                         Compositions     (Preferred)                                                                             (Broad)                                            ______________________________________                                        Viscosity Modifier                                                                             .01-4     0.01-12                                            Detergents       0.01-3    0.01-20                                            Corrosion Inhibitor                                                                            0.01-1.5  .01-5                                              Oxidation Inhibitor                                                                            0.01-1.5  .01-5                                              Dispersant       0.1-8      .1-20                                             Pour Point Depressant                                                                          0.01-1.5  .01-5                                              Anti-Foaming Agents                                                                            0.001-0.15                                                                              .001-3                                             Anti-Wear Agents 0.001-1.5 .001-5                                             Friction Modifiers                                                                             0.01-1.5  .01-5                                              Mineral Oil Base Balance   Balance                                            ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the novel dispersants of this invention (inconcentrate amounts hereinabove described), together with one or more ofsaid other additives (said concentrate when constituting an additivemixture being referred to herein as an additive-package) whereby severaladditives can be added simultaneously to the base oil to form thelubricating oil composition. Dissolution of the additive concentrateinto the lubricating oil may be facilitated by solvents and by mixingaccompanied with mild heating, but this is not essential. Theconcentrate or additive-package will typically be formulated to containthe additives in proper amounts to provide the desired concentration inthe final formulation when the additive-package is combined with apredetermined amount of base lubricant. Thus, the dispersants of thepresent invention can be added to small amounts of base oil or othercompatible solvents along with other desirable additives to formadditive-packages containing active ingredients in collective amounts oftypically from about 2.5 to about 90%, and preferably from about 15 toabout 75%, and most preferably from about 25 to about 60% by weightadditives in the appropriate proportions with the remainder being baseoil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein (unless otherwiseindicated) are based on active ingredient (A.I.) content of theadditive, and/or upon the total weight of any additive-package, orformulation which will be the sum of the A.I. weight of each additiveplus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight, unless otherwise notedand which include preferred embodiments of the invention.

EXAMPLE OF THE PREPARATION OF POLYANILINE GRAFTED POLYMERS

Example 1

(a) A solution of 2.3 g (0.01 mol) ammonium peroxydisulfate (NH₄)₂ S₂ O₈! in 150 ml 1M HCl was stirred at room temperature. 16 grams ofpolyisobutylene-NH₂ (PIB-NH₂) (PIB M_(n) 2200) (0.73 wt. % N) wasdissolved in 50 ml THF and was mixed with 4.85 g (0.052 mol.) ofaniline, employing a charge ratio of 6.2:1 moles of aniline per reactiveamine molar equivalent. This amine solution was added to the acidicoxidizing solution and the polymerization product solution was stirredfor 6 hours. The precipitate was then collected by filtering and waswashed with about 200 ml of 1 M HCl until the filtrate became colorless.The solid residue was dissolved in 400 ml of xylene, filtered andsolvent was removed from the filtrate by distillation. The productobtained was dried in vacuum oven at room temperature for 24-48 hours.The dried polymer product was found to contain 1.0 wt. % N.

(b) To convert the grafted polyaniline hydrochloride obtained in (a)above into the polyaniline base form, the hydrochloride was suspended inaqueous NH₄ OH (approximately 100 ml of 0.1M aqueous solution of NH₄ OHwere used per gram of the hydrochloride) with stirring for 16 hours atroom temperature. The pH of the solution was periodically adjusted toca. 10 (pH paper test) by the addition of a small amount of 1M NH₄ 0H.The suspension was then filtered and the precipitate was washed with ca.400 ml of 0.1M NH₄ OH followed by five 50 ml portions of a 1:1 mixtureof methanol and 0.2M NH₄ OH. The polymer base so prepared was driedunder dynamic vacuum at room temperature for 48 hours. The dried polymerproduct was found to contain 1.55 wt. % N.

Example 2

Using the procedure of Example 1(a), a solution of 4.6 g (0.02 mol)ammonium peroxydisulfate (NH₄)₂ S₂ O₈ ! in 200 ml 1M HCl was stirred atroom temperature. 7.5 grams of PIB-NH₂ was dissolved in 100 ml THF andwas mixed with 9.3 g (0.1 mol) of aniline, to provide ananiline:reactive amine equivalent molar charge ratio of about 25:1. Thisamine solution was added to the acidic oxidizing solution and wasallowed to stir. The reaction was exothermic and temperature of thereaction went up to the 50° C. The solution was allowed to stir for 6hours. After ca. 6 hrs., the precipitate was collected and was washeduntil the filtrate became colorless using about 200 ml of 1M HCl . Thesolid residue was dissolved in 400 ml of xylene, filtered and thesolvent was removed from the filtrate by distillation. The graft polymerobtained was further stirred with 200 ml of 1M HCl to ensure completedoping. The product was filtered and dried in vacuum oven at roomtemperature for 24-48 hours. The dried product contained 4.53 wt. % Nand its two probe conductivity was 3×10⁻³ S/cm.

Example 3

(a) Using the procedure of Example 1(a), a 100 grams of the PIBSA-PAMdispersant product prepared as in Example R was mixed with 4.6 g (0.02mol) ammonium peroxydisulfate (NH₄)₂ S₂ O₈ ! and 200 ml 1M HCl and wasstirred at room temperature. 1 gram (0.0107 mol) of aniline was addedslowly the above solution (to provide an aniline:reactive amineequivalent molar charge ratio of about 0.4:1) and was allowed to stirfor 6 hours. After ca. 6 hrs., the precipitate was collected and waswashed until the filtrate became colorless using about 200 ml of 1M HCl.The product was dried in vacuum oven at room temperature for 24-48hours.

(b) The convert grafted polyaniline hydrochloride into polyaniline base,the hydrochloride was suspended in aqueous NH₄ OH (approximately 100 mlof 0.1M aqueous solution of NH₄ OH were used per gram of thehydrochloride) with stirring for 16 hours at room temperature. The pH ofthe solution was periodically adjusted to ca. 10 (pH paper test) by theaddition of a small amount of 1M NH₄ OH. The suspension was thenfiltered and the precipitate was washed with ca. 400 ml of 0.1M NH₄ OHfollowed by five 50 ml portions of a 1:1 mixture of methanol and 0.2MNH₄ OH. The polymer base was dried under dynamic vacuum at roomtemperature for 48 hours.

GRAFT CHARACTERIZATION

Ultraviolet-Visible Spectroscopy is a useful technique to characterizeconjugated polymers such as the polyaniline grafted polymers of thisinvention. FIG. 1 shows the solution electronic absorption spectra ofpolyaniline grafted PIB-NH₂ of Example 1 recorded in hexane solution, inthe neutral state (product of Example 1(b)) and in the doped state(product of Example 1(a)). These spectra were spectra of true solutionsas evidenced by the fact that there was no evidence of deposition orprecipitation of solid, when solutions were kept undisturbed over aperiod of two weeks. Unlike the grafted polymers of this invention, thehomopolymer of polyaniline is not soluble in hexane or other typicalorganic solvents. The spectra of polyaniline homopolymer which have beenreported in the literature (Wudl, F.; Angus, R. O.; Lu, F. L.; Allemend,P. M.; Vachon, D. J.; Nowak, M.; Liu, Z. X.; Heeger, A. J., J. Am. Chem.Soc. 1987, 109, 3677) polyaniline and polyaniline.HCl, showcharacteristic peaks at the 620 nm and 820 nm, respectively. However,these spectra were obtained for colloidal suspensions which are notstable, and in the case of homopolymer of polyaniline, a deposition ofgreen precipitate is seen even in DMF, leaving a completely colorlesssolution within 12 hours.

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art withoutdeparting from the spirit of the invention.

What is claimed is:
 1. A lubricating oil composition containing fromabout 0.1 to 20 wt. % of an oil-soluble dispersant and antioxidantadditive which comprises an N-containing polymer adduct comprising thereaction product of a polyalkylene polyamine with a polymer substitutedwith mono- or dicarboxylic acid, anhydride or ester groups, wherein saidN-containing polymer adduct has been grafted in the presence of aneffective amount of an oxidizing agent, by polymerizing thereon at leastone aromatic N-monomer represented by the formula:

    Ar' NH(R.sup.b)!y'

wherein Ar' is ##STR13## wherein R^(c) in each instance in which itappears is independently C₁ to C₁₂ alkyl, y' is an integer of from 1 to4, y" is an integer of from 0 to 4, y'" is an integer of from 0 to 4, Din each instance in which it appears is independently Cl, Br or I, R^(b)is hydrogen or C₁ to C₂₀ alkyl, and Z¹ is a branched or straight chainalkylene group which can contain one ore more --O-- or --S-- chainatoms, with the proviso that the sum of y+y'+y'" is from 1 to
 5. 2. Alubricating oil composition according to claim 1 containing from about0.1 to 8 wt. % of the additive.